EXCHANGE 


The  University  of  Chicago 

Founded  by  JOHN  D.  ROCKEFELLER 


The  Preparation  of  Optically- Active  Hydra- 
zines.     I.   The   Preparation  of  J/-p-Tri- 
methylethylphenylhydrazine.    The  Iso- 
lation of  Pure  c/-p-Trimethylethyl- 
Aniline 


A  DISSERTATION 


SUBMITTED  TO  THE  FACULTY  OF  THE  OGDEN  GRADUATE 

SCHOOL  OF  SCIENCE  IN  CANDIDACY  FOR  THE 

DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


DEPARTMENT  OP  CHEMISTRY 


By  CHARLES  H.  MILLIGAN 


EASTON,  PA.: 

PRESS  OF  THE  ESCHENBACH  PRINTING  CO. 
1920 


The  University  of  Chicago 

Founded  by  JOHN  D.  ROCKEFEU.BR 


The  Preparation  of  Optically-Active  Hydra- 
zines.     I.    The   Preparation  of  J/-p~Tri~ 
methylethylphenylhydrazine.    The  Iso- 
lation of  Pure  J-p-Trimethylethyl- 
Aniline 


A  DISSERTATION 


SUBMITTED  TO  THE  FACULTY  OF  THE  OGDEN  GRADUATE 

SCHOOL  OF  SCIENCE  IN  CANDIDACY  FOR  THE 

DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


DEPARTMENT  OF  CHEMISTRY 


By  CHARLES  H.  MILLIGAN 


EASTON,  PA.: 

PRESS  OF  THE  ESCHENBACH  PRINTING  CO. 
1920 


THE    PREPARATION    OF     OPTIC  ALLY- ACTIVE     HYDRAZINES. 

I.     THE  PREPARATION  OF  d/-£-TRIMETHYLETHYL- 

PHENYLHYDRAZINE.     THE  ISOLATION  OF 

PURE  d-^-TRIMETHYLETHYL-ANILINE.1 

In  connection  with  the  preparation  of  the  optically-active  C4-sacchar- 
inic  acids  undertaken  in  this  laboratory  it  was  found  that  success  depended 
in  each  case  on  the  ability  to  resolve  the  d/-acid  into  the  components  by 
means  of  optically-active  alkaloids.  Such  separations  are  usually  very 
tedious,  require  many  recrystallizations,  and  sometimes  leave  one  in  doubt 
as  to  whether  a  complete  separation  has  actually  been  effected.  It  has 
seemed  highly  desirable,  therefore,  to  make  available  other  reagents  than 
the  alkaloids  for  such  work. 

Phenylhydrazine  is  known  to  form  with  many  oxyacids  easily  crystal- 
lizable  compounds,  the  phenylhydrazids.  Some  of  the  homologs  such  as 
tolyl-hydrazine  form  at  times  even  more  easily  crystallizable  compounds. 
It  was  thought,  therefore,  that  an  optically-active  phenylhydrazine  might 
be  a  possible  substitute  for  the  alkaloids  when  the  latter  do  not  give  good 
results  or  when  there  is  any  doubt  as  to  the  completeness  of  the  resolu- 
tions. 

A  search  in  the  literature  of  optically-active  hydrazines  disclosed  the 
fact  that  only  3  such  compounds  have  been  prepared,  namely,  d-a-opti- 
cally-active  amyl -phenylhydrazine;2  /-a-ethyl-menthylhydrazine,3  and 
/-menthylhydrazine.4  The  few  known  derivatives  of  these  substances 
indicated  that  they  might  be  very  helpful  in  work  with  the  oxyacids. 

None  of  the  hydrazines  mentioned  above  was  available,  however,  and 
it  was  decided  to  attempt  the  preparation  of  a  number  of  racemic  phenyl- 
hydrazines,  and  the  resolution  of  these  into  active  isomers  in  the  hope  that 
in  this  work  some  fairly  easily-prepared  active  hydrazine  would  be  dis- 
covered which  could  be  used  as  a  reagent  in  the  separation  of  the  sac- 
charinic  acids  to  supplement  the  alkaloids. 

The  present  paper  is  the  report  of  an  attempt  to  prepare  the  first  pair 
of  these  hydrazines  decided  upon,    namely,    the    active    trimethylethyl- 
phenylhydrazines.     The  hydrazine  in  its  dl  form  was  prepared,  but  all 
1  Reprinted  from  an  article  in  the  Journal  of  theAmerican  Chemical  Society    for 
November,  1920,  by  J.  W.  E.  Glattfeld  and  C.  H.    Milligan 
1  Ber.,  38,  867  (1905)- 

1  /.  Russ.  Phys.  Chem.  Soc.,  27,  534  (1896). 
4  J.  Prakt.  Chem.,  II,  52,  425  (1895). 


4581714 


attempts  to  resolve  it  into  the  components  failed,  due  largely,  we  think, 
to  the  instability  of  the  free  hydrazine  in  the  air  under  ordinary  conditions. 
The  instability  of  the  dl  form  suggested  that  the  active  components  would 
also  be  very  unstable  and  thus  be  useless  as  reagents.  On  the  other  hand, 
some  of  the  derivatives  of  the  dl  form  (see  below)  are  perfectly  stable 
compounds,  and  it  was  thought  possible  that  the  derivatives  of  the  active 
forms  would  also  be  stable.  We  therefore  decided  to  proceed  with  at- 
tempts to  obtain  the  active  forms.  After  much  experimentation  one  of 
the  amines,  d-£-trimethylethyl  -aniline,  was  obtained  in  the  pure  condi- 
tion. It  was  intended  to  prepare  from  this  the  corresponding  active 
phenylhydrazine  by  diazotization  and  reduction  but  time  was  lacking  to 
complete  this.  This  work  will  be  continued,  however,  as  soon  as  oppor- 
tunity offers  and  attempts  will  be  made  to  prepare  other  active  phenyl- 
hydrazines. 

Experimental  Part. 

This  paper  is  a  report  on  the  preparation  of  d/-£-trimethylethyl-phenyl- 
hydrazine. 

H      H  H       H 


H,C  —  C  —  C  —  <          >  —  N  —  N  —  H 

I     I 

CH,   CH, 

In  order  to  prepare  this  substance,  it  was  necessary  first  to  prepare,  in 
turn,  the  following  corresponding  compounds:  (i)trimethylphenyl  -ethyl  - 
ene;  (2)  trimethylethyl  -benzene  ;  (3)  ^-trimethylethyl-  nitrobenzene;  (4)p- 
trimethy  lethyl-aniline  . 

Only  the  second  of  these  compounds  is  mentioned  in  the  literature,  under 
the  name  of  seowdary-amyl-benzene.1  It  seems  probable  in  the  light  of 
our  experiments,  however,  that  the  compound  there  discussed  was  tertiary- 
amyl-benzene. 

For  purposes  of  report,  the  work  done  and  results  obtained,  will  pos- 
sibly be  most  easily  followed  if  we  discuss,  in  the  order  in  which  they  are 
listed  above,  the  preparation  of  the  necessary  compounds. 

i.  Trimethylphenyl-ethylene.  —  This  compound  was  prepared  from 
magnesium  iso-propyl  iodide  and  acetophenone  by  a  modification  of  the 
method  used  by  Klages2  devised  by  Grignard.3  The  magnesium  iso- 
propyl  iodide  was  made  in  the  usual  way  with  all  ordinary  precautions 
by  carefully  dropping  i'so-propyl  iodide  into  ether  containing  magnesium 
turnings.  The  ether  was  stirred  constantly  by  a  mechanical  stirrer  and 
kept  cold.  At  the  end  of  the  reaction  the  solution  was  allowed  to  come 
to  the  temperature  of  the  room  and  was  then  forced  away  from  the  re- 

1  Ann.  Chim.  phys.,  [6]  i,  454  (1884);  Monatsh.,  9,  622  (1888). 
8  Klages,  Ber.,  35,  2641  (1902);  33,  439  (1900). 
1  Grignard,  Compt.  rend.,  130,  1322  (1900). 


maining  magnesium  turnings  and  into  another  flask  properly  fitted  up 
and  protected  against  moisture,  etc. 

Acetophenone  was  then  carefully  dropped  into  the  solution  with  stirring. 
The  end  of  the  reaction  was  reached  when  the  heat  of  reaction  was  not 
sufficient  to  keep  the  solution  boiling.  We  found  this  condition  to  pre- 
vail after  about  1/2  the  theoretical  amount  of  acetophenone  had 
been  added.  It  had  been  found  in  preliminary  experiments  that  further 
addition  of  acetophenone  did  not  increase  the  yield  and  could  be  recovered 
unchanged.  The  mixture  was  then  kept  at  the  boiling  temperature, 
with  stirrer  operating,  for  from  2  to  3  hours.  The  ether  was  then  distilled 
off,  after  which  the  thick  pasty  residue  was  heated  on  the  boiling  water- 
bath  for  from  4  to  6  hours.  The  mass  was  then  allowed  to  cool,  the 
stirrer  started  and  water  carefully  added  from  the  dropping  funnel.  When 
all  the  mass  had  been  completely  hydrolyzed,  the  mixture  was  extracted 
3  or  4  times  with  ether.  The  ether  solution  was  dried  with  sodium  sul- 
fate  and  fractionated.  The  part  which  boiled  between  175-200°  was  col- 
lected. This  fraction  weighed  1 25  g.  when  100  g.  of  acetophenone  was  used. 

In  order  to  isolate  the  hydrocarbon  in  a  pure  state,  this  fraction  (175— 
200°)  was  refractionated  and  the  part  which  boiled  at  187-188°  collected- 
This  fraction,  in  alcohol,  was  treated  with  phenylhydrazine,  and  the 
hydrazone  of  acetophenone,  formed  on  standing,  was  removed  by  filtra- 
tion. The  filtrate  was  fractionated  at  18  mm.  pressure  and  the  fraction 
of  boiling  range  75-95°  was  dissolved  in  a  little  dry  ether  and  treated 
with  dry  hydrogen  chloride  to  remove  phenylhydrazine.  The  filtrate 
from  the  phenylhydrazine  hydrochloride  was  subjected  to  repeated  frac- 
tionation  and  gave  finally  5.6  g.  of  a  colorless  liquid  which  boiled  at  187- 
188°.  The  analysis  of  samples  of  this  liquid  showed  that  the  compound 
thus  prepared  was  not  methyHso-propyl-phenyl-carbinol,  but  trimethyl- 
phenyl  -e  thy  lene . 

Subs.,  0.1167,  0.1217:  COz,  0.3871,  0.3982;  U-zO,  0.0989,  0.1032. 

Calc.  for  CnHi4:  C,  90.35;  H,  9.65.     Found:  C,  90.60,  90.70;  H,  9.40,  9.44. 

2.  Trimethylethyl-benzene. — The  next  step  was  to  reduce  the  un- 
saturated  hydrocarbon  to  the  saturated  one.  One  hundred  and  twenty-five 
g.  of  the  crude  trimethyl-phenyl^ethylene  (boiling  range  175-200°)  was 
treated,  in  a  flask  fitted  with  a  wide  reflux  condenser,  with  30  g.  of  red 
phosphorus  and  50  cc.  of  a  saturated  solution  of  hydrogen  iodide.  The  re- 
action mixture  was  heated  to  boiling  and  iodine  added  carefully  in  small 
portions  through  the  condenser  until  fumes  due  to  escaping  hydrogen  iodide 
were  visible  at  the  top  of  the  condenser.  The  mixture  was  kept  boiling  until 
the  color  due  to  iodine  in  the  hydrocarbon  disappeared.  The  reaction  mix- 
ture was  now  subjected  to  distillation.  The  distillate  formed  2  layers  of 
almost  equal  volume  of  which  the  lower  was  hydriodic  acid,  the  upper 
almost  pure  hydrocarbon.  The  layers  were  separated,  the  hydriodic  acid 


returned  to  the  reaction  flask,  and  again  distilled.     This  process  was  re- 
peated as  long  as  any  hydrocarbon  separated  in  the  distillate. 

The  hydrocarbon  was  then  washed  with  water  and  dil.  sodium  hydrox- 
ide solution  and  dried  first  by  calcium  chloride  and  finally  over  melted 
sodium  which  removed  also  the  last  trace  of  iodine,  and  then  fractionated. 
That  portion  (40  g.)  boiling  at  180-190°  was  used  for  the  subsequent 
preparations,  a  part  being  refractionated  a  number  of  times  in  order  to 
get  a  pure  product.  The  fraction  boiling  at  1 86-1 88  °  was  considered  pure. 

Analysis  of  a  sample  of  this  product  (186-188°)  gave  the  following 
results : 

Subs.,  0.1688:  CO2,  0.5503;  H2O,  0.1602. 

Calc.  for  CnHjj:  C,  89.12;  H,  10.88.     Found:  C,  88.9;  H,  10.69. 

3.  ^-Trimethylethyl-nitrobenzene. — Forty  g.  of  trimethylethyl-ben- 
zene  boiling  at  180-190°  was  dissolved  in  24  g.  of  glacial  acetic  acid  and 
added  drop  wise  to  a  constantly  stirred  mixture  of  40  g.  of  glacial  acetic  acid1 
and  88  g.  of  fuming  nitric  acid  kept  at  35-40°.  After  the  addition,  the 
contents  of  the  flask  were  kept  at  50°  for  3  hours,  cooled  and  poured  into 
twice  the  volume  of  cold  water.  The  nitro  compound  thus  obtained  was 
extracted  with  low-boiling  ligroin,  and  the  ligroin  extract  repeatedly  shaken 
with  water  and  finally  with  a  small  amount  of  sodium  carbonate  solution 
and  then  dried  over  sodium  sulfate  and  fractionated.  A  yield  of  46  g. 
of  nitro  compound,  boiling  range  140-155°  at  20  mm.  pressure,  was  ob- 
tained.2 After  a  number  of  fractionations,  this  gave  30  g.  boiling  at 
152-154°  under  20  mm.  pressure.  This  fraction  was  considered  pure 
substance  and  was  used  for  analysis  and  for  the  determination  of  the 
position  of  the  nitro  group. 

Subs.,  0.2147:  COa,  0.5423;  H2O,  0.1508. 

Subs.,  0.2557,  0.2835:  Nj,  18.2  cc.  (29°  and  737.4  mm.),  19.1  cc,  (25°  and  736.9 
mm.). 

Calc.  for  CuH18NO,:  C,  68.38;  H,  7-80;  N,  7.29.  Found:  C,  68.37;  H,  7.8;  N, 
7.51,  7.44. 

Position  of  the  Nitro  Group. — One  g.  of  the  compound  was  treated 
in  the  usual  way3  with  10  g.  of  chromic  acid  dissolved  in  25  cc.  of  5  N 
acetic  acid.  This  mixture  was  allowed  to  stand  for  24  hours  on  a  steam- 
bath,  and  gave,  after  filtration,  solution  in  sodium  hydroxide  and  repre- 
cipitation  with  hydrochloric  acid,  0.7  g.  of  crude  substance  with  melting 
range  228-230°.  After  recrystallization  from  water,  the  crystals  had  a 

1  Ann.,  327,  224  (1903). 

*  From  the  fraction  which  had  the  boiling  range  130-132°  there  was  obtained  a 
small  amount  of  white  crystalline  solid  which  had  a  melting  point  of  114-115°.     In 
repetitions  of  the  nitration  crystals  of  the  same  melting  point  were  usually  obtained 
from  this  fraction.     The  almost  invariable  production  of  this  compound  led  to  the  con- 
clusion that  it  was  the  0-nitro-compound, 

*  Weyl,  "Die  Methoden  der  Organischen  Chemie,"  1909,  Vol.  I,  518. 


sharp  melting  point  of  236°.  A  sample  of  ^-nitrobenzoic  acid  at  hand 
melted  sharply  at  236°.  Furthermore  a  mixed  melting-point  determina- 
tion proved  the  two  to  be  identical.  The  compound  oxidized,  therefore, 
had  the  nitro  group  in  the  para  position  to  the  trimethylethyl  group. 

4.  ^-Trimethylethyl-aniline. — A  mixture  of  23  g.  of  the  nitro  com- 
pound, 36  g.  of  tin  and  75  cc.  of  cone,  hydrochloric  acid  was  warmed  to 
1 00°,  kept  near  this  temperature,  and  very  frequently  shaken  until  the  odor 
of  the  nitro  compound  had  almost  entirely  disappeared.     The  remaining 
nitro  compound  was  removed  by  steam  distillation.     The  residue  was 
made  alkaline  with  sodium  hydroxide,  although  a  large  excess  of  alkali 
is  to  be  avoided.     The  aniline  was  extracted  with  low-boiling  ligroin, 
dried  over  anhydrous  sodium  carbonate,  and  fractionated  repeatedly  at 
1 8  mm.  pressure.     There  was  obtained  finally  16  g.  of  a  colorless  oil  of 
boiling  range  129-131°  at  18  mm.  pressure. 

That  the  substance  was  the  pure  aniline  was  proved  by  the  analysis 
of  samples  for  nitrogen. 

Subs.,  0.1853,  0.2225  g.:N2,  H-5  cc-  (22°  and  736.6  mm.),  17.4600.  (19° and  731-3 
mm.). 

Calc.  for  CnHnN:  N,  8.57.     Found:  8.76,  8.75. 

5.  d^-Trimethylethyl-phonylhydrazine. — This  compound  was  made 
by  a  modification  of  the  method  of  Fischer.1     Fifteen  g.  of  the  aniline  was 
diazotized,  forming  a  gelatinous  mass  which  was  added  in  small  amounts 
to  a  cold  solution  of  sodium  sulfite.     A  light  yellow  crystalline  solid  was 
obtained.     The  cold  reaction  mixture  was  treated  with  zinc  dust  and 
acetic  acid  until  the  yellow  color  had  disappeared.     The  sulfonate  thus 
obtained  was  filtered  off,  together  with  the  excess  of  zinc  dust,  etc.,  and 
purified  by  crystallization  from  hot  water,  giving  19  g.  of  white  plates 
which  decomposed  when  heated  to  190°. 

The  hydrochloride  of  the  hydrazine  was  prepared  by  dissolving  the 
sulfonate  in  a  small  amount  of  boiling  water  and  passing  hydrogen  chloride 
into  this  hot  solution.  As  the  solution  cooled,  the  hydrochloride  crystal- 
lized out  in  rosets  of  fine  white  needles  which  were  perfectly  stable  when 
dry. 

The  hydrochloride  was  dissolved  in  water  and  treated  with  sodium 
hydroxide.  The  solution  was  extracted  with  ether  and  the  ether  removed 
by  distillation.  The  hydrazine  separated  out  in  fine  needles  as  the  residue 
cooled.  This  residue  was  subjected  to  distillation  at  9  mm.  pressure  in 
an  atmosphere  of  hydrogen.  There  was  thus  obtained  9  g.  of  a  slightly 
yellow  compound  of  boiling  range  147-150°  at  9  mm.  which  soon  entirely 
solidified.  The  solid  had  a  melting  point  of  about  60°,  and  was  soluble 
in  alcohol,  ligroin,  benzene  but  less  soluble  in  ether  than  in  any  of  these. 
In  contact  with  the  air  a  part  of  this  solid  soon  turned  red  and  in  the 
1  Ann.,  190,  78  (1877). 


8 

course  of  a  few  hours  liquefied.     When  this  substance  is  kept  in  an  atmo- 
sphere of  hydrogen,  decomposition  takes  place  very  slowly,  if  at  all. 

Samples  of  this  solid  were  quickly  weighed  and  analyzed,  with  the  fol- 
lowing results : 

Subs.,  0.2085,  0.0698  g. :  N2,  28  cc.  (19°  and  735.2  mm.),  14.9  cc.  (28°  and  730.25 
mm.). 

Calc.  for  CnHi8N2:  N,  15.78.     Found:  15.62,  15.66. 

As  stated  above,  it  was  found  impossible  to  resolve  the  hydrazine  into 
the  optical  components.  Several  attempts  were  made  to  do  this  and  some 
data  have  been  accumulated.  It  was  shown,  for  instance,  that  the  hy- 
drazine reacts  with  the  sugars  to  form  hydrazones  or  osazones  and  that 
it  reacts  with  oxyacids  such  as  Z-erythronic,  d-mannonic  and  d-gluconic 
acids.  From  the  study  of  these  derivatives,  however,  it  did  not  seem 
likely  that  the  racemic  hydrazine  could  be  resolved  completely  by  the  use 
of  such  compounds  although  some  evidence  of  resolution  was  obtained. 
The  hydrazine  forms  a  particularly  stable  and  well-crystallizing  com- 
pound, m.  p.  160-163°,  presumably  the  hydrazid,  with  d-galactonic  lactone. 
The  Resolution  of  d/-£-Trimethylethyl-aniline. 

The  resolution  was  finally  accomplished  by  the  use  of  J-oxymethylene 
camphor1  according  to  the  method  of  Pope  and  Read,2  as  follows. 

Sixteen  and  five-tenths  g.  of  the  aniline  was  dissolved  in  25  cc.  of  30% 
acetic  acid  and  added  slowly  and  with  shaking  to  a  solution  of  17.5  g. 
of  J-oxymethylene  camphor  in  70  cc.  of  methyl  alcohol.  The  yellow  oil 
which  separated  out  as  a  lower  layer  was  shaken  a  number  of  times  with 
water,  then  dissolved  in  as  small  a  quantity  of  boiling  alcohol  as  possible 
and  reprecipitated  from  the  cold  solution  with  water.  The  liquid  was 
decanted  after  the  pasty  mass  had  settled  out  completely.  The  latter 
was  stirred  thoroughly  with  dil.  sodium  hydroxide  solution  then  with  water 
and  finally  taken  up  in  a  little  alcohol,  and  placed  in  a  vacuum  desiccator 
over  sulfuric  acid.  After  having  stood  for  2  days,  the  residue  was  a  semi- 
crystalline  mass  weighing  30.9  g.  The  specific  rotation  of  this — pre- 
sumably a  mixture  of  equal  parts  of  the  isomers — was  found  to  be  +257.5°. 
Subs.,  0.6922  in  15.68  g.  of  95%  alcohol  gave  in  a  2  dcm.  tube  a  +17-82. 

The  mass  was  now  treated  with  ligroin  until  most  of  the  gummy  ma- 
terial was  removed  and  there  remained  a  slightly  yellow  solid,  which,  after 
having  been  thoroughly  air-dried,  weighed  18.9  g.  and  which  had  a  melt- 
ing range  of  156-158°.  This  product  was  twice  recrystallized  from  boil- 
ing alcohol,  and  was  then  perfectly  white.  It  weighed  8.2  g.  A  portion 
of  it  was  dissolved  in  95%  alcohol.  The  specific  rotation  of  this  solution 
was  determined  as  +300°. 

Subs.,  0.6540  in  20  cc.  of  95%  alcohol   gave  in  a  2  dcm.  tube  a  +19.69°  at  25-26*. 

1  Ann.,  281,  333  (1894). 

2  Pope  and  Read,  J.  Ch&m.  Soc.,  95,  171  (1909). 


This  product  was  recrystallized  3  times  from  alcohol.  The  specific 
rotation  was  taken  after  each  recrystallization  and  always  found  to  be 
+300°,  indicating  that  the  compound  was  pure.  The  product  now  melted 
sharply  at  168°. 

Pure  d-£-Trimethylethyl-aniline. — Forty  g.  of  the  product  obtained 
as  indicated  above  was  heated  at  boiling  for  30  hours  with  225  cc.  of 
cone,  hydrochloric  acid  and  then  cooled.  The  liquid  was  decanted  from 
the  solid  and  evaporated  to  dryness  on  a  steam-bath.  The  total  solid  thus 
obtained  was  treated  with  2po  cc.  of  strong  sodium  hydroxide  solution  and 
subjected  to  steam  distillation  as  long  as  any  oil  came  over.  The  distil- 
late was  made  acid  and  evaporated  on  the  steam-bath,  the  aniline  set 
free  again  and  distilled  with  steam,  this  process  being  repeated  several 
times  in  order  to  purify  the  aniline.  There  was  finally  obtained  n.6 
g.  of  the  hydrochloride.  This  was  treated  with  an  excess  of  sodium 
hydroxide  solution,  the  aniline  thoroughly  extracted  with  low-boiling 
ligroin  and  the  ligroin  solution  dried  with  sodium  carbonate.  The  ligroin 
was  removed  by  distillation  and  the  residue  distilled  at  24  mm.  pressure. 
The  distillate  had  a  boiling  range  of  139-140°  and  weighed  8:6  g.  When 
placed  in  a  one  dcm.  tube,  this  oil  gave  a  -{-0.96°.  The  hydrochloride 
was  prepared  by  dissolving  the  aniline  in  ligroin  and  passing  in  hydrogen 
chloride.  An  air-dry  sample  of  the  hydrochloride  thus  prepared  had  a 
specific  rotation  of  +0.974. 

Subs.,  1.0294  in  20  cc.  of  water  containing  3  drops  of  cone,  hydrochloric  acid,  gave 
in  a  2  dcm.  tube  a  +  o.io. 

/-^-Trimethylethyl-aniline. — We  were  unable  to  obtain  the  more 
soluble  derivatives  of  the  aniline  with  d-oxymethylene  camphor  in  the 
crystalline  condition.  When  the  filtrates  from  the  crystalline  derivative 
were  evaporated  to  dryness  and  dried  over  sulfuric  acid  in  vacuo,  a  few 
more  crystals  of  the  less  soluble  isomer  separated.  These  were  re- 
moved by  treatment  of  the  mass  with  ligroin,  in  which  the  crystals  did 
not  dissolve.  A  gum  was  finally  obtained  which  did  not  deposit  crystals 
on  standing  in  a  vacuum  over  sulfuric  acid  for  10  days,  [a]^?  4-229,  in 
95%  alcohol.  The  aniline  from  this,  obtained  as  above,  boiled  at  139- 
140°  and  gave  a  — 0.76  when  placed  in  a  one  dcm.  tube.  The  hydro- 
chloride  gave  [a]™ — 0.565.  These  figures  show  that  the  aniline  was  not 
perfectly  pure. 

Summary. 

d/-£-Trimethylethyl-phenylhydrazine,  and  d/-£-trimethylethyl-aniline 
have  been  prepared,  some  of  their  properties  determined  and  the  latter 
partly  resolved  into  the  two  optical  isomers.  The  hydrazine  was  pre- 
pared from  acetophenone  and  magnesium-isopropyl-iodide  and  making, 
successively,  trimethyl-phenyl-ethylene,  trimethylethyl-benzene,  £-tri- 
methylethyl-nitrobenzene,  £-trimethylethyl-aniline. 


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